EP0142578B1

EP0142578B1 - A method of encapsulating gases, vapors, complexes and ions in solids

Info

Publication number: EP0142578B1
Application number: EP83201517A
Authority: EP
Inventors: Etiènne Vansant; Paul De Bièvre; Guido Jozef Peeters; Anita Thijs; Ingrid Verhaert
Original assignee: European Atomic Energy Community Euratom
Current assignee: European Atomic Energy Community Euratom
Priority date: 1983-10-21
Filing date: 1983-10-21
Publication date: 1988-08-24
Also published as: US4569683A; EP0142578A1; DE3377770D1

Description

This invention relates to a method of encapsulating compounds in fibrous of layer silicates. It is known that fibrous clays belonging to the palygorskite group, such as sepiolite, can adsorb gases or other materials and that they can also take in ions by ion exchange. Very important for the sorption properties of the material are the degassing conditions. When degassed at 100°C in vacuo, physically sorbed water is removed, but no structural change occurs and sorption of gas molecules between the hexagonal sheets is possible. At higher degassing temperatures a distortion of the lattice occurs, restricting the access to the channels in the structure, and resulting in a sharp decrease in the sorptive capacity (A. J. Dandy; J. Chem. Soc. (A) 1971, Inorg. Phys. Theor., pp. 2383-2387). In the present invention a reorientation of the structural units by a thermal modification is used for trapping adsorbed gas molecules.
A purely physical adsorption or ion exchange, is always a reversible process, so that an adsorbed gas is slowly or rapidly released spontaneously upon contact with atmospheric air, and ions can be liberated upon contact with aqueous solutions.
For the above reason such a simple adsorption or ion exchange is unsuitable for fixing undesirable materials definitively and in a stable manner, or for storing desirable substances in a simple and effective manner.
In U.S. Patent 3,316,691, it is proposed to encapsulate gases or fluids in a suitable zeolite, whose pores are not large enough to take in the molecules concerned at room temperature and atmospheric pressure. In that process a gas or a liquid, e.g. argon, krypton or methane, is adsorbed in the zeolite at a high pressure, e.g. 2000 bar and a high temperature, e.g. 250-350°C. After completion of adsorption, the whole is cooled to room temperature and the pressure is released. It turns out that thereafter the adsorbed gas is only very slowly released again at room temperature. Desorption proceeds at a higher rate at a high temperature, for example at the temperature used during the adsorption.
According to the patent, this slow desorption is due to a potential barrier at the entrance of the pores. It is more probable, however, that the adsorbed molecules can only escape from the pores by diffusion, which always proceeds at a slow rate, and goes on continuously until all of the gas has been desorbed. Although it is proposed in the patent to use this method for storing adsorbed gases for a longer or shorter period of time, it is accordingly clear that this is only practicable, if the regular escape of a portion of such gases is not objectionable. Also the encapsulation requires much energy.
The European patent application 29875 describes a method for encapsulating gas molecules under high pressures and high temperatures in zeolites. The encapsulation is based on a thermal vitrification of the zeolite in presence of pressurized gas. Under this pressure, and at higher temperature, the zeolite transforms into an amorphous stable material, containing the enclosed gas molecules. This process ag'ain requires high pressures and temperatures, and therefore much energy.
The European patent application 49936 describes the possibility to encapsulate gas molecules and other molecules by closing or narrowing the zeolitic pores after sorption under normal conditions of temperature and pressure. The pore size reduction is obtained by a structural modification process, based on chemisorption of a modifier such as SiH₄, etc. followed by further reaction with O2, H ₂0, CH₃0H, etc.
The present invention is based thereon, that gase molecules are trapped in a palygorskite group clay, such as sepiolite between the hexagonal sheets of the structure, by distorting the lattice in the presence of gas molecules. This distortion can be obtained by thermal dehydration action with or without modifying agents such as B₂H₆ or others.
According to the present invention the process for permanently encapsulating a gas or a gas mixture in a clay material belonging to the palygorskite group comprising

partially dehydrating the clay material under conditions that substantially no structural changes occur,
adsorbing the gas to be encapsulated in the partially dehydrated clay material, and
heating the clay with the adsorbed gas, while in contact with the gas to be adsorbed, at a temperature causing a collapse of the palygorskite structure under conditions resulting in permanent encapsulation of the gas or gas mixture between the hexagonal sheets of the structure.

By a pure thermal treatment, the sepiolite is first degassed at 100°C-130°C, preferably at 100110°C under vacuum for removing physically adsorbed water. Then gas is allowed to the vessel, containing the clay under a pressure between 1 and 20 bar. Subsequent heating of the material, which is still in contact with the gas, causes a further dehydration and a reorientation of the structure units resulting in encapsulation of the enclosed gas molecules (hereafter called "collapsing temperature"). The thermal treatment results in the loss of water, according to the following scheme:

2H20(ads)+[H20]g{Mgs(H20)4(OH)4[Si1203o]} (example of sepiolite)
- -2H₂0(ads), -8H ₂0 reversible loss of zeolitic and adsorbed water
- -4H ₂0 removal of crystal water, irreversible change of the structure

The values of T₁ and T₂ depend on the nature and the pressure of the surrounding gas. In air, for example, T₁ and T₂ are 250°C and 350/450°C respectively. In contrast wtih the high pressure/high temperature encapsulation, as reported in EP-A 29875, the structural collapse is not caused by a high pressure effect, but is the result of a dehydration, occurring at any pressure. Moreover when increasing the gas pressure, a higher temperature is required before a structural collapse occurs. Increasing the pressure therefore has a thermal disadvantage, but increases the loading capacity of the encapsulate.
In addition, the encapsulation temperature (collapsing temperature) depends on the size of the gas molecules to be encapsulated: larger molecules require higher temperatures. The blocking of the desorption can be enhanced by treating the sample with B₂H_s. Because of its reactivity with water (hydration and structural), chains of -O-B-O- bonds are formed, resulting in an additional structural change of the mineral. The reaction with structural hydroxyl groups results in chemisorption of BH₂ qroups:
These groups react further with other OH groups:
Further reaction with water can occur:
or
The reaction with water will occur with any type of water: crystal water, zeolitic water, adsorbed water. The manner in which diborane forms O-B-O bonds by hydrolysis depends on the pretreatment conditions before B₂H₆ is reacted with the substrate. Depending on the degree of hydration, different combinations of reactions (1) to (4) occur and different interconnecting O-B-O bonds are possible. As a result boranation of partly dehydrated samples and thermal dehydration leads to structural change with different properties. Using a combination of dehydration and boranation, encapsulation of gas molecules can be performed at lower treatment temperatures (collapsing temperature).

Example I

Encapsulation of Kr in sepiolite by thermal treatment .

A sample of sepiolite was activated at 110°C under vacuum. Then the krypton was added to the sepiolite at 20°C and 2 bar. The Kr-sepiolite system was heated to 450°C. After the thermal treatment the remaining gases were evacuated and the sample was kept under a static vacuum. The thermal stability of the Kr-sepiolite system was checked by gradually raising the temperature of the sample, collecting the released gases fractionally and analysing them by mass spectrometry.
The results are given below: (shown in Figure 1):
The total amount of Krypton which had been encapsulated was 2 liters (STP) per kg of sepiolite.

Example II

a) The influence of the nature of the gas molecules on the collapsing temperature

A sample of sepiolite was heated stepwise from 20°C to 350°C under vacuum. During this heating no adsorbed gases were present. After each temperature interval the adsorption of gaseous Ar, N₂ and O2 at -196°C was carried out to study the remaining adsorption capacity. Depending on the nature of the gas molecules different collapsing temperatures were observed (Figure 2) at which this capacity sharply decreased (Figure 2)
While these collapsing temperatures merely define the steepest point in the relative curves, the curves themselves, shown in Fig. 2 make it clear that a dramatic change occurs at about 150°C, whenever a sepiolite on which no gas has been adsorbed, is heated.

b) The influence of the pressure on the collapsing temperature

In this experiment a sepiolite was heated on which argon had been adsorbed. The sample was heated under an argon pressure of 0,133 bar and the heating temperature was stepwise increased from 20°C to 350°C.
After each heating the sample was cooled under argon pressure to room temperature, then the argon present was pumped off until a vacuum was obtained. At room temperature there is no danger of collapsing, either in the presence or in the absence of argon.
After this evacuation the adsorption capacity of the sample for argon was determined at -196°C in order to establish whether or not a collapse had taken place during the heating.
The results are shown in Fig. 3 (curve B). It turns out that the steepest decline in adsorption capacity occurs at about 350°C as compared with 150°C forthe same sample when it was heated in a vacuum (curve A is shown in both Fig. 2 and Fig. 3). It would then seem that the adsorbed argon molecules support the structure of the sepiolite and delay the collapse.

Example III

Encapsulation of Kr in sepiolite by a combined thermal-and chemical modification procedure

A sepiolite sample was activated (dehydrated) by a thermal treatment at 110°C in a vacuum. After a chemisorption of diborane at 20°C, krypton was added at 20°C and 2 bar. The Kr-modified sepiolite system was heated to 450°C to collapse the sepiolite. The stability of Kr-sepiolite system was then tested in a static vacuum at various temperatures by collecting all the released gases fractionally and analysing them by mass spectrometry.
The results are given below: (Figure 4)
The total encapsulated amount of Krypton was 10 liters (STP) per kg sepiolite.

Example IV

Encapsulation of Xe in sepiolite by a combined thermal chemical modification procedure

A sepiolite sample was activated by a thermal treatment at 110°C in a vacuum. After a chemisorption of 0,80 mmol diborane per gram sepiolite at 20°C, Xe was added at 0°C and 3 bar. The Xe-loaded sepiolite was heated to 480°C. The stability of the Xe-sepiolite system was then tested in a static vacuum at various temperatures by collecting all the released gas fractions and analysing them by mass spectrometry.
The results are given below (Fig. 5).
The total amount of encapsulated xenon was 15 liters (STP) per kg sepiolite.

Claims

1. Process for permanently encapsulating a gas or a gas mixture in a clay material belonging to the palygorskite group, comprising

partially dehydrating the clay material under conditions that substantially no structural changes occur,

adsorbing the gas to be encapsulated in the partially dehydrated clay material, and

heating the clay with the adsorbed gas, while in contact with the gas to be adsorbed, at a temperature causing a collapse of the palygorskite structure under conditions resulting in permanent encapsulation of the gas or gas mixture between the hexagonal sheets of the structure.

2. Process according to claim 1, wherein the clay material is partially dehydrated in vaccum.

3. Process according to claim 2, wherein the partial dehydration is carried out at 100-130°C.

4. Process according to claim 1, wherein the clay material is partially dehydrated in the presence of a . gas.

5. Process according to claim 4, wherein the clay material is partially dehydrated in the presence of the gas to be adsorbed.

6. Process according to claims 1-5, wherein the partially dehydrated clay material has been chemically modified with diborane.

7. Process according to claims 1-6, wherein sepiolite is used as the clay material.

8. Process according to claims 1-7, wherein the clay with the adsorbed-gas is heated at a temperature of at least 150°C.